CN106715759B - Electrolytic cell is used in the manufacture of organic chemistry hydride - Google Patents
Electrolytic cell is used in the manufacture of organic chemistry hydride Download PDFInfo
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- CN106715759B CN106715759B CN201580051360.7A CN201580051360A CN106715759B CN 106715759 B CN106715759 B CN 106715759B CN 201580051360 A CN201580051360 A CN 201580051360A CN 106715759 B CN106715759 B CN 106715759B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
It provides: can be with high current efficiency and small electric power consumption rate carries out has the organic chemistry hydride manufacture electrolytic cell of reduction reaction of the organic compound of unsaturated bond at cathode.Electrolytic cell (10) are used in a kind of manufacture of organic chemistry hydride, are had: the solid polyelectrolyte membrane (11) with proton-conducting；It is set to a face of solid polyelectrolyte membrane (11) and the cathode (12) that object restores and generates hydride will be hydrogenated；It stores cathode (12) and is supplied to the cathode chamber (13) for being hydrogenated object；It is set to another face of solid polyelectrolyte membrane (11) and water oxygen is generated to the anode (14) containing electrode catalyst of proton；With, storage anode (14) and the anode chamber (15) for being supplied to electrolyte, at least one of cathode (12) side surface and anode (14) side surface of solid polyelectrolyte membrane (11) have carried out hydrophiling.
Description
Technical field
The present invention relates to the manufactures of organic chemistry hydride with electrolytic cell (hereinafter, being also referred to simply as " electrolytic cell "), in detail and
Speech, is related to: can be with high current efficiency and small electric power consumption rate carries out having the organic compound of unsaturated bond in yin
Electrolytic cell is used in the organic chemistry hydride manufacture of reduction reaction at pole.
Background technique
The electric power consumption of Japan is 1000TWh or so every year, currently, thermal power generation also takes on nuclear electric power generation amount, because
This, the ratio of thermal power generation reaches 90%.On the other hand, as inhibiting the new energy of CO2 emissions, it is expected that too
The renewable energy such as positive energy, wind-force, waterpower, geothermal power generation are popularized, but its generation power amount is only whole at this stage
1% or so.Although Japan benefits from water resource, about solar energy, wind-force, it is difficult to say it is suitable soil, status is, no
It obtains independent of from external energy delivery and storage.In addition, positive consider to generate electricity based on wind-power electricity generation and large solar
It is changed to alleviate short-period output, but is difficult to use in macrocyclic output variation, extensive energy delivery in alleviation.Therefore recognize
Effectively, to convert chemical energy source for the electric power obtained by these renewable energy.Electric power is converted into chemical energy
The technique in source is electro-chemical systems, and secondary cell, so-called battery are the equipment for converting electric power to chemical energy source and storing,
Through being widely used.
As the system based on renewable energy, following system is promising: in global suitable soil
Large-scale solar power generation, wind generator system are set, and conversion is conveyed to energy carrier, to consume the energy at home.
As energy carrier, it is contemplated that liquid hydrogen, ammonia, organic chemistry hydride etc..However, hydrogen is gas in normal temperature and pressure, have conveying,
Storage needs the shortcomings that special oil carrier etc.In this case, using hydrocarbon such as hexamethylene, hexahydrotoluene, naphthalanes
Organic chemistry hydride replaces the conveying of hydrogen, storage to attract attention.
As organic chemistry hydride, if the liquid that selection is similar with the character of petroleum, has the following advantages: with it is larger
The compatibility of the system of scale is excellent, in addition, the dispatching until the end of energy resource system is also easy.That is, these organise
Learn hydride is liquid at normal temperatures and pressures, is easily processed, by that will be used as the organic compound of raw material electrochemically
It is hydrogenated, dehydrogenation, to can be used as energy carrier storage, transport instead of hydrogen.
In the past, it in the manufacture of the organic chemistry hydride such as hexahydrotoluene, carries out: by renewable energy utilization water electrolysis
And hydrogen is manufactured, toluene is hydrogenated in hydrogenation reactor and is converted into hexahydrotoluene, but if being electrolytic synthesis, then
Technique can be made to simplify and directly being hydrogenated.In addition, electrolysis organic chemistry hydride manufacturing method no matter scale
If what loss in efficiency is all few, the tracing ability for starting stopping is excellent.Further, in the system comprising high-temperature technology, hold in efficiency
On the foothold of the renewable energy of the small-scale easily reduced, especially in terms of efficiency, it can advantageously carry out the energy and turn
Change, and carries to the energy of organic chemistry hydride and store transmission net.
The technology of organic chemistry hydride as using has carried out various researchs so far.For example, patent
It is proposed in document 1,2, about the electrolytic cell that will there is the organic compound of unsaturated bond to restore.In addition, patent document
3, propose in 4, about use membrane separation device from the device of organic compound manufacture hydrogen.Further, it is proposed in patent document 5
, supply about hydrogen is manufactured from organic compound to the device of fuel cell.In turn in addition, being proposed in patent document 6,7,
About the electrolytic oxidation of organic compound, the method for reduction.
On the other hand, in salt electrolysis industry, by carrying out electrolysis to salt using the septate type electrolytic cell of Room 2,
Chlorine, sodium hydroxide and hydrogen are manufactured simultaneously.However, it is necessary to which electrode is closely configured with diaphragm, and decomposition voltage is reduced, therefore
It has been known that there is following so-called bubble effects: the bubbles attached on hydrophobic film surface, and bucking current and obstructive substance move
It is dynamic, cause the increase of cell voltage.In particular, the hydrogen generated in the amberplex of fluorine system, chlorine are easy in the form of bubble
Attachment, when especially making electrode at a distance from film close to 2mm or less, due to bubble influence and it has been known that there is: on decomposition voltage
It rises, hydrogen is easy to attach in film (non-patent literature 1) compared with chlorine.In order to solve the problems, by the way that membrane surface is hydrophilic
Change, inhibits attachment of the bubble generated to diaphragm, do not make bubble residence near electrode-membrane, to realize decomposition voltage
It reduces.(such as patent document 8~13)
Existing technical literature
Patent document
Patent document 1: Japanese Patent Application 2014-069716
Patent document 2:WO2012-091128
Patent document 3:US2008-234527A
Patent document 4:US2009-025291A
Patent document 5:US6802875B
Patent document 6:US2014-110268A
Patent document 7:WO13-134220A1
Patent document 8: Japanese Unexamined Patent Publication 1981-075583
Patent document 9: Japanese Unexamined Patent Publication 1981-145927
Patent document 10: Japanese Unexamined Patent Publication 1981-152980
Patent document 11: Japanese Unexamined Patent Publication 1982-039185
Patent document 12: Japanese Unexamined Patent Publication 1984-219487
Patent document 13: Japanese Unexamined Patent Publication 1991-137136
Non-patent literature
Non-patent literature: the 2009 Japan's Soda industry of Soda technical manual can p58
Summary of the invention
Problems to be solved by the invention
In the manufacture of organic chemistry hydride, in order to which anode chamber's liquid of aqueous solution will be used as and as organic compound
Cathode chamber liquid is kept completely separate, it is necessary to use dielectric film.In electrolysis organic chemistry hydride method so far, at anode
The oxygen of generation and the hydrogen generated in the form of side reaction at cathode are attached to dielectric film, therefore part generates electric current
Unevenness homogenize, interfere the reduction of the unsaturated compounds at cathode as a purpose, cause the loss of voltage.It is organic as manufacturing
The example of the reduction reaction of the organic compound with unsaturated bond when chemical hydride, it is described below: with toluene (TL) work
Carry out the formula of reduction synthesis hexahydrotoluene (MCH) for raw material.
Cathode reaction:
TL+6H++6e-→MCH
Anode reaction:
2H2O→4H++4e-+O2
Overall reaction:
2TL+6H2O→2MCH+3O2
In this way, in the same manner as salt electrolysis, in the manufacture of organic chemistry hydride with also generating bubble effect in electrolytic cell, but
Status is, not yet to the film surface processing technique of salt electrolysis in the electrolysis process other than salt electrolysis whether effectively into
Row research.In particular, obvious in high current by the loss of voltage caused by bubble effect.
Therefore, the object of the present invention is to provide: can be with high current efficiency and small electric power consumption rate is had
There is the organic chemistry hydride manufacture electrolytic cell of reduction reaction of the organic compound of unsaturated bond at cathode.
The solution to the problem
The inventors of the present invention have made intensive studies to eliminate the above subject, as a result, it has been found that: by making dielectric film
Surface so far completes the present invention for defined structure so as to eliminate the above subject.
That is, organic chemistry hydride manufacture electrolytic cell of the invention is characterized in that having: with proton-conducting
Solid polyelectrolyte membrane；Cathode is set to a face of the solid polyelectrolyte membrane and will be hydrogenated object reduction
And generate hydride；Cathode chamber, stores the cathode and is supplied to and be hydrogenated object；Anode containing electrode catalyst, is set to
Another face of aforesaid solid polyelectrolyte membrane and water oxygen is generated into proton；With, anode chamber, store the anode,
And it is supplied to electrolyte,
At least one of said cathode side surface and aforesaid anode side surface of aforesaid solid polyelectrolyte membrane into
Hydrophiling is gone.
It is aforementioned hydrophilic to turn to aforesaid solid polyelectrolyte membrane in organic chemistry hydride manufacture electrode of the invention
Surface it is further provided for contouring in the case where, as long as make 30 μm of maximum height in the JIS B 0601 by further provided for contouring surface with
It is lower, it, can be in the case that the aforementioned hydrophilic surface for turning to aforesaid solid polyelectrolyte membrane is using inorganic layer covering
Make 0.005~10 μm of average grain diameter of primary particle in aforementioned inorganic nitride layer containing 30~95 mass %, and makes aforementioned inorganic
The overlay capacity of nitride layer is 0.01~10mg/cm2.In addition, in organic chemistry hydride manufacture electrode of the invention, it is aforementioned primary
Particle is preferably selected from least one kind of in the oxide, nitride and carbide of the periodic table of elements the 4th, 5,13 or 14 race's elements.
Further, in organic chemistry hydride of the invention manufacture electrode, the thickness of aforementioned inorganic nitride layer is preferably 1~80 μm.This
Place, average grain diameter refer to, utilize the average grain diameter D of laser diffractometry measurement50。
The effect of invention
According to the present invention, the hydrogen generated at the oxygen or cathode generated at the anode in organic chemistry hydrogenation material producing device
Gas is not easy to be attached to dielectric film, can prevent current convergence, can also restore with the organic of unsaturated bond under high currents
Compound.As a result, can provide: can be with high current efficiency and small electric power consumption rate carries out having unsaturated bond
The organic chemistry hydride manufacture electrolytic cell of reduction reaction of the organic compound at cathode.
Detailed description of the invention
Fig. 1 is that the summary of the organic chemistry hydride manufacture electrolytic cell of a suitable embodiment of the invention is constituted
Figure.
Fig. 2 is that the electric current of the electrolytic cell of the embodiment 1,2 when showing the output voltage 2.0V for making constant voltage power supply is close
The figure of the ongoing change of the current density of the electrolytic cell of the ongoing change and comparative example 1 of degree.
Fig. 3 is the current density and ratio for showing the electrolytic cell for the embodiment 3 for making decomposition voltage from 0.6V frequency sweep to 3.8V when
Compared with the figure of the current density of the electrolytic cell of example 1~3.
Specific embodiment
Hereinafter, using attached drawing, detailed description of embodiments of the present invention.
Fig. 1 is that the summary of the organic chemistry hydride manufacture electrolytic cell of a suitable embodiment of the invention is constituted
Figure.Electrolytic cell 10 of the invention has: the solid polyelectrolyte membrane with proton-conducting is (hereinafter also referred to as " electrolyte
Film ") 11；It is set to a face of dielectric film 11 and the cathode 12 that object restores and generates hydride will be hydrogenated；Store cathode
12 and it is supplied to the cathode chamber 13 for being hydrogenated object；It is set to another face of dielectric film 11 and water oxygen is generated into proton
The anode 14 (hereinafter, being also referred to simply as " anode ") containing electrode catalyst；With store and anode 14 and be supplied to electrolyte
Anode chamber 15.In illustrated example, cathode 12 is made of cathode substrate 12a with the cathode catalyst layer 12b for being formed in its surface.
In addition, in illustrated example, cathode chamber 13 is by outermost partition 13a and is configured at peripheral part and the electricity of partition 13a
The spacer 13b solved between plasma membrane 11 is constituted, and there are cathode support body 12c between partition 13a and cathode 12.Further,
Anode chamber 15 is by the spacer between outermost partition 15a and the peripheral part and dielectric film 11 that are configured at partition 15a
15b is constituted.And then in addition, anode-supported elastomer 14a is configured between partition 15a and anode 14, in anode 14 and electricity
It solves and is configured with anode spacer 16 between plasma membrane 11.In addition, in illustrated example, it is provided in the lower part of cathode chamber 13 and is hydrogenated object and enters
Mouth 17 is provided with hydride outlet 18 on the top of cathode chamber 13, the lower part of anode chamber 15 is provided with acidic electrolyte bath entrance
19, the top of anode chamber 15 is provided with acidic electrolyte bath outlet 20.
In electrolytic cell 10 of the invention, at least one of 14 side surface of 12 side surface of cathode and anode of dielectric film 11
Hydrophiling is carried out.By forming above-mentioned composition, the oxygen generated at the hydrogen or anode 14 generated at cathode 12 is not easy to adhere to
In dielectric film 11, current convergence can be prevented, the organic compound with unsaturated bond can also be restored under high currents.This
In the electrolytic cell 10 of invention, the method for the hydrophiling on the surface as dielectric film 11 can be enumerated: the surface of dielectric film 11
It is further provided for contouring, utilize inorganic layer cover 11 surface of dielectric film.Hereinafter, the composition to electrolytic cell of the invention carries out specifically
It is bright.
[solid polyelectrolyte membrane]
As dielectric film 11 used in electrolytic cell 10 of the invention, preferably by molten to oxidation reaction, organic compound
The long-time stability of agent are excellent, fluororesin prepared material with sulfonic acid as ion-exchange group is formed.Dielectric film 11 by
Material (ionomer) formation with proton-conducting, selectively proton conducting, another aspect are electrolysed one side dielectric film 11
11 inhibiting substances of plasma membrane are mixed or spread between cathode 12 and anode 14.The thickness of dielectric film 11 is preferably 5~300
μm, more preferably 10~200 μm, particularly preferably 20~100 μm.When the thickness of dielectric film 11 is lower than 5 μm, dielectric film 11
Barrier property reduce, be easy to produce crossover leaks.In addition, ion moving resistance becomes when the thickness of dielectric film 11 is greater than 300 μm
Too much, it is not preferable.
In electrolytic cell 10 of the invention, as described above, concaveconvex shape is assigned by the surface to dielectric film 11, so as to
To carry out hydrophiling, in addition, the surface covering inorganic layer to dielectric film 11 can also carry out hydrophiling, alternatively, it is also possible to
They are applied in combination.By the way that the surface of dielectric film 11 is carried out hydrophiling, it can prevent cathode 12, generate in anode 14
Attachment of the gas to 11 surface of dielectric film.Hydrophilicity-imparting treatment can be any in the anode-side to dielectric film 11 or cathode side
Surface is implemented, and can also be implemented to two sides.Under above situation, the hydrogen for being possible to generate at cathode 12 can be prevented to be electrolysed
Accumulation in plasma membrane 11, aftermentioned cathode porous material improves electrolysis performance, selectivity.
Herein, the mechanism for preventing attachment of the gas to dielectric film 11 is illustrated.The drop of the surface of solids is with solid
When body (S)-liquid (L)-gas (V) coexists and balances, for surface tension γ, Young's equation is set up.
γ SV=γ SL+ γ LVcos θ, θ: the contact angle of liquid versus solid
When using water as liquid, the big surface for being 90 ° or more θ is known as hydrophobicity, θ is claimed close to 0 surface
For hydrophily.In addition, surface be it is uniformly but geometrically uneven and there are when roughness, in apparent contact angle θ ' and practical
Contact angle between Wenzel formula set up.
Cos θ '=rcos θ, r: actual surface area/apparent surface product >=1
This refers to, if it is θ>90 °, θ<θ ', that is, when by being not easy wet wheat flour into asperities, become to be less susceptible to moisten,
If it is θ<90 °, θ>θ ', that is, when by being easy wet wheat flour into asperities, become easier to moisten.General commercially available ion
The contact angle θ of the water of exchange membrane is 90 ° hereinafter, when the surface of amberplex therefore being carried out further provided for contouring, is held according to the latter
It is easily wet.Therefore it estimates, the attachment of the oxygen generated by water electrolysis on the surface of the film being not easy to cause in anode 14.Similarly,
The contact angle of organic system solution and film in cathode 12 is also 90 ° hereinafter, presumption can be effectively prevented the attachment of the hydrogen of generation.
As the method that the surface to dielectric film 11 assigns concaveconvex shape, for example: use sand paper or paste
The grinding agent of shape, by 0.001 μm~10 μm of surface grinding of method of dielectric film 11.About sand paper or grinding agent, such as sand
No. 2000 sand paper can be used in paper, and the grinding agent that abrasive grain diameter is 0.3 μm can be used in grinding agent.11 surface of dielectric film it is recessed
Convex, i.e. surface roughness maximum height is preferably 30 μm hereinafter, more preferably 0.01 μm or more and 15 μm or less.Herein, most
Big height refers to, the maximum height in JIS B 0601.
When the surface of dielectric film 11 is covered with inorganic layer, it is preferred that primary containing 30~95 mass %
The inorganic layer at least one kind of particles of inorganic material that the average grain diameter of grain is 0.005~10 μm, preferably 0.01~0.015 μm.On
In the case of stating, it is preferred that by the every 1cm of inorganic layer2Cover 0.01~10mg or so.Inorganic layer is preferably comprised by having parent
30~95 mass % of 5~70 mass % of adhesive and particles of inorganic material that aqueous fluorine system polymer is constituted.
As the primary particle for constituting inorganic layer, it is preferably selected from the oxygen of the periodic table of elements the 4th, 5,13 or 14 race's elements
It is at least one kind of in compound, nitride and carbide.Particularly preferably zirconium, silicon and titanyl compound, nitride or carbide.
In electrolytic cell 10 of the invention, the thickness of the inorganic layer on 11 surface of dielectric film is preferably 1~80 μm, more preferably
It is 5~30 μm.This is because, the thickness of inorganic layer is greater than 80 μm, the effect based on hydrophiling does not also change substantially, separately
Outside, it when the thickness of inorganic matter film is lower than 1 μm, is unable to fully obtain the effect of hydrophiling sometimes.
, can be closely sealed by anode 14, cathode 12 and dielectric film 11 in electrolytic cell 10 of the invention, can also as shown that
Sample configures anode spacer 16 between dielectric film 11 and anode 14, thus between being formed between anode 14 and dielectric film 11
Gap.Alternatively, it is also possible to similarly form gap between cathode 12 and dielectric film 11.
[cathode]
In electrolytic cell 10 of the invention, as illustrated, cathode 12 can be by cathode substrate 12a and cathode catalyst layer
12b is constituted.As the cathode substrate 12a for the cathode 12 for constituting electrolytic cell 10 of the invention, can be used: by as porous, electrically conductive
Property substrate the fiber sinterings body such as cloth, paper etc. that is formed of carbon.Using the reasons why porous conductive substrate be due to, for gas and
The supply of liquid removes, and preferably has porosity appropriate and keeps sufficient electrical conductance.It is particularly preferred that with a thickness of
0.01~5mm, porosity are 30~95%, representative aperture is 0.001~1mm.It should be noted that in the cathode substrate
When metal component has coexisted in the surface of 12a, the electric conductivity of conductive layer entirety is improved, and reaches the homogenization of electric current, therefore it is preferred that.
Carbon cloth is the fine carbon for counting μ m diameter to be made to hundreds of beams and by obtained from its woven fabric, gas-liquid permeability
It is excellent, it is preferred as cathode substrate 12a therefore.In addition, carbon paper is using paper method processed using carbon raw material fiber as film
Precursor and obtained from being sintered, can also be suitble to use.When directly powering to the carbon electrical conductivity substrate, not due to it
Sufficient electric conductivity, therefore cause the concentration of local of electric current, the electricity locally concentrated is also supplied with into gas diffusion layers, conversion zone
It flows and reduces electrolytic efficiency, but by the way that metal component coexists, electric current can be supplied uniformly across to conductive substrate.
[cathod catalyst]
As the type of cathod catalyst, the metal in platinum, ruthenium, palladium, iridium or their alloy can be used
Grain.Commercially available particle also can be used in they, can also be synthesized according to known methods, and carried out using.For example,
Synthesis can be using the damp process for mixing reducing agent in the aqueous solution for dissolving catalyst metal ion and synthesizing, can also
Using dry methods such as vapor deposition, sputterings.The partial size of cathod catalyst particle is preferably 0.001~1 μm.
Cathod catalyst particle is not necessarily required to be carried on cathode substrate 12a, but by using carbon particle as carrier
Grain, is unfolded, so as to effectively expand catalyst surface area on the particle.As carrier granular, usually used carbon particulate,
Furnace black, acetylene black etc. can be used.The partial size of carbon particulate is preferably 0.01~1 μm.Electroconductive powder in conversion zone has suppression
The function of hydrophilic catalyst particle aggregation processed.
[manufacture of cathode]
The manufacturing method of cathode 12 is not particularly limited.For example, by catalyst component powder, hydrophobic resin, water, stone
Cerebrol equal solvent, Nafion (registered trademark) dispersion liquid DE521 (DuPont system) mixing as ionomer, with the matter after drying
It measures and is added with the mode for the ratio that the carbonaceous quantitative change in catalyst is 1:10~10:1, suitably use solvent, preparation coating
Catalyst ink.Later, which is coated on cathode substrate 12a and drying, roasting, so as to so that cathode catalysis
The particle of agent is bonded to cathode substrate 12a.The ionomer of Nafion dispersion liquid is for maintaining non-leading inside cellular structure body
The electronics mobile response that electrical organic hydride closes in object is effective.Hydrophobic resin (fluorine ingredient) is gas-premeable material,
As the partial size of the powder, preferably 0.005~10 μm.It is coated and dried, roasts when being divided into multiple implementation, available homogeneous
Cathode catalyst layer 12b, therefore it is preferred that.In this way, the cathode 12 with cathode catalyst layer 12b can be made.
In electrolytic cell 10 of the invention, catalyst ink ingredient also can be used, form cathode catalysis on dielectric film 11
Oxidant layer.Also it can use bar coater rubbing method, form cathode catalyst layer in the single side of dielectric film 11, cathode-electrolysis is made
Plasma membrane complex.The catalyst ink can also be become every electrode area with the quality of Pt and Ru in adduction catalyst is
0.5mg/cm2Mode be sprayed on dielectric film 11, the solvent composition in ink is dry, obtain dielectric film-catalyst
Conjugant.
Cathode substrate 12a is used due to applying pressure to thickness direction, and thus the electric conductivity of thickness direction changes
It is undesirable.In order to improve performance and the cathode of the filling rate with 20~50% be made, pressure processing is preferably implemented.Pressurization
The purpose of processing is, improves its electric conductivity and compressing to carbon material, and make apply pressure and using when fill out
Fill rate and stable conductivity variation.The conjugation grade of cathode catalyst layer 12b and cathode substrate 12a improves, while being also beneficial to lead
Electrically improve.In addition, compression and cathode catalyst layer 12b and cathode substrate 12a due to cathode substrate 12a and conversion zone
Conjugation grade raising, the supply of raw material and the removing ability for generating substance increase.As pressure processing device, Ke Yili
The device well known to hot press, hot-rolling etc..As pressurized conditions, at room temperature~360 DEG C, pressure is desired for 0.1~5MPa.Such as
Upper operation can be manufactured with high electric conductivity and reactive cathode 12.
[anode]
As the anode base material for the anode 14 for constituting electrolytic cell 10 of the invention, required electricity is electrolysed for flowing through from having
It sets out in terms of sufficient electric conductivity, the necessity for the mechanical strength for constituting electrolytic cell 10 for stream, is preferably made thickness
The board-like material of 0.1mm to 2mm.Gas generates in electrode, and in order to avoid being increased by resistance caused by bubble, promotion is electrolysed
The supply of liquid, preferably porous body commonly use the porous sieve of titanium system to the excellent corrosion resistance of acidic electrolyte bath.Become after sieve processing
For three-dimensional structure, therefore suitably carry out smoothing techniques.It is expected that the optimum thickness range of porous sieve is 0.1~2mm, short side side
It is 0.1~4mm to distance between centers, longitudinal direction distance between centers is 0.1~6mm, and aperture opening ratio is 30~70% or so.
[manufacture of anode]
The manufacture of anode 14 is preferably, and carries out dry-type jetting processing to the surface of the titanium as anode base material, then into
Cleaning treatment in the aqueous solutions such as 20% sulfuric acid of row.Later, using arc ion plating apparatus on 14 surface of anode through over cleaning
Form titanium-tantalum layer etc..This is because, titanium-based material inhibits the corrosion occurred in electrolysis.As titanium-tantalum layer thickness, preferably
0.1~10 μm.Later, will be coated with dissolved with the mixed aqueous solution of iridium (Ir) and tantalum ingredient, then in electric furnace implementation 360~
The operation is repeated as many times by 550 DEG C of heat treatment, so as to manufacture anode.In the anode of electrolytic cell of the invention, it can incite somebody to action
Reach 1~40g/m in terms of the conversion of the Ir amount of metal of every electrode area2Mode form the electrode formed by yttrium oxide and tantalum oxide
The material of catalyst layer is compatibly used as anode 14.
[pool structure]
The most external of the cathode chamber 13 of electrolytic cell 10 of the invention shown in Fig. 1 is equipped: with electronic conductivity
Partition 13a.Partition 13a is for example formed by metals such as stainless steels.It is equipped between the peripheral part and dielectric film 11 of partition 13a
Spacer 13b becomes cathode chamber 13 by the space that partition 13a, spacer 13b and dielectric film 11 are surrounded.Spacer 13b is simultaneous
Having prevents the organic matter comprising being hydrogenated object and hydride to the sealing element of 13 external leakage of cathode chamber, is contemplated to be electronic isolation
's.As the material of spacer 13b, for example: tetrafluoroethylene resin.
In illustrated example, it is equipped in the lower part of spacer 13b and is hydrogenated object entrance 17, be hydrogenated object entrance 17 to cathode from this
Room 13 supplies toluene etc. and is hydrogenated object.In addition, being equipped with hydride outlet 18 on the top of spacer 13b, go out by the hydride
The organic matter of the hydride such as hydride, that is, hexahydrotoluene comprising toluene is expelled to outside system by mouth 18.
In addition, being equipped with cathode support body 12c between partition 13a and cathode 12 in illustrated example.Cathode support body 12c
As be described hereinafter, by the power squeezed by anode-supported with elastomer 14a, it is ensured that the electronic conductivity between partition 13a and cathode 12.
In addition, cathode support body 12c also forms the flow path that control is hydrogenated the flowing of object and hydride.
It is equipped in the outside of the anode chamber 15 of electrolytic cell 10 of the invention: the partition 15a with electronic conductivity.Partition
15a is for example formed by metals such as titaniums.Between being equipped between the peripheral part and dielectric film 11 of 14 side surface of anode of partition 15a
Spacing body 15b becomes anode chamber by the space that partition 15a, the spacer 15b of 15 side end of anode chamber and dielectric film 11 are surrounded
15.Spacer 15b has the sealing element for preventing acidic electrolysis bath to 15 external leakage of anode chamber concurrently, is contemplated to be electronic isolation.Make
For the material of spacer 15b, for example: tetrafluoroethylene resin etc..
In illustrated example, the lower part of spacer 15b be equipped with acidic electrolysis bath entrance 19, from the acidic electrolysis bath entrance 19 to
Anode chamber 15 supplies acidic electrolysis bath.As acidic electrolysis bath, can enumerate: the ionic conductivity measured at 20 DEG C is 0.01S/
Sulfuric acid, phosphoric acid, nitric acid or the hydrochloric acid of cm or more.When the ionic conductivity of acidic electrolysis bath is lower than 0.01S/cm, industrially it is difficult to
Obtain sufficient electrochemical reaction.In addition, acidic electrolysis bath outlet 20 is equipped on the top of spacer 15b, by acidity electricity
Liquid outlet 20 is solved, the acidic electrolysis bath being stored in anode chamber 15 is expelled to outside system.
In addition, being configured with anode-supported elastomer 14a between anode 14 and partition 15a in illustrated example, utilizing anode
Support is squeezed anode 14 to dielectric film 11 with elastomer 14a.Anode-supported is with elastomer 14a for example by flat spring, coil
The electronic conductor of structure is formed.In illustrated example, there are anode spacers 16 between anode 14 and dielectric film 11, utilize
Anode spacer 16 is constituted in the way of keeping defined gap between anode 14 and dielectric film 11.In this way, constituting
Anode-supported elastomer 14a is set between the partition 15a and anode 14 of anode chamber 15 and forms the structure for keeping anode 14, from
And the upkeep operations such as the exchange of anode 14 can be made to be easy.
Anode-supported elastomer 14a is preferably acidproof by having to the acidic electrolysis bath flowed into from acidic electrolysis bath entrance 19
The material of property is formed, as substrate, it is preferable to use titanium or titanium alloy.As the elastomer for constituting anode-supported elastomer 14a
Structure, it is contemplated that (fiber is by vibrating patterning method for V-shape spring, X cloth spring, the type of buffer coil, chatter mark fiber
(chatter vibration cutting method) manufacture) the various structures such as aggregate.Face pressure needed for each is in view of each
The contact resistance of component and suitably select material thickness etc..
Embodiment
Hereinafter, the embodiment of the present invention is described in detail, but these embodiments are only for compatibly illustrating this
The example of invention, is not limited in any way the present invention.
<embodiment 1>
Had using NRE212CS (DuPont system, 25 μm of thickness) in anode-side surface formation as dielectric film
The zirconium oxide layer of 5 μ m-thicks simultaneously carries out hydrophiling.When forming the cathode catalyst layer in the cathode-side surface of dielectric film, firstly,
In PtRu/C catalyst TEC61E54E (Tanaka's noble metal industrial group system, Pt23 mass %, Ru27 mass %) powder, with
The mode that carbonaceous amount in quality and catalyst after drying reaches 4:5 mass adds ionomer Nafion (registered trademark) dispersion
Liquid DE521 (DuPont system), the appropriate ink using solvent preparation coating.By the ink in adduction catalyst Pt and
The quality of Ru is 0.5mg/cm relative to electrode area2Mode be sprayed on dielectric film, then will be in ink at 70 DEG C
Solvent composition is dry and obtains cathode catalyst layer, as cathode catalyst layer-dielectric film conjugant.
In gained cathode catalyst layer-dielectric film conjugant cathod catalyst layer surface, paste and electrode surface phase
The cathode diffusion layer SGL35BC (SGL Carbon system) of symbol ground punching, carries out handling for 2 minutes at 120 DEG C, 1MPa, forms yin
Pole-dielectric film complex.
As the structural body for being bonded to cathode separator and cathode support body, using to carbon/epoxy resin carried out mold at
The carbon architecture body of type.The cathode support body portion of the structural body forms multiple for liquid on the face contacted with cathode diffusion layer
The flow path of body circulation, the flow path 1 hole portion with width 1mm, path heights 0.5mm, be between flow path between be divided into the straight of 1mm
Wire shaped is configured so that vertical direction when organic chemistry hydride manufacturing device is arranged with flow path as parallel mode.
In addition, the both ends of the flow path of structural body have the liquid collectors for merging multiple flow paths and supplying and being discharged for liquid, by it
It is connect with the path of the supply of organic matter and discharge.
As anode base material, thickness 1.0mm, short side direction distance between centers 3.5mm, longitudinal direction distance between centers are used
The porous sieve of 6.0mm.Dry-type jetting processing is carried out to the surface of anode base material, is then cleaned in 20% aqueous sulfuric acid
Processing.Later, using arc ion plating apparatus and titanium-tantalum alloy plate, with 2 μm at 150 DEG C of base material temperature, vacuum degree 1.3Pa
Coating thickness cover the surface of the anode base material through over cleaning.For the obtained anode base material, be coated with iridic chloride/
The mixed aqueous solution of tantalic chloride then implements 550 DEG C of heat treatment in electric furnace, which is repeated as many times, thus will be by
Become 12g/m according in terms of the conversion of the Ir amount of metal of every electrode area2Mode form the electrode formed by yttrium oxide and tantalum oxide
The material of catalyst layer is as anode.
As anode-supported elastomer, using such as lower elastic body: being formed obtained from the Ti plate for making to process thickness 0.3mm
The shape of the coach spring arrangement of 10mm spacing.Micro platinum layer is formed on the positive contact face of coach spring.
By these pond component, i.e. cathode support bodies, cathode-electrolyte film conjugant, anode, anode-supported elastomer according to
Secondary stacking is inserted into anode-supported elastomer, thus using in the pond scope fixed between the partition and anode of anode-side
The interior extruding force from anode-side is squeezed in the mode that each layer is closely sealed.It should be noted that the thickness of anode spacer is set
It is 25 μm.
In the cathode chamber of the obtained electrolytic cell, making toluene, vertically (lifter) circulates from bottom to up, separately
Outside, in the hole portion (anode chamber) between anode and the partition of anode-side, similarly make 5% aqueous sulfuric acid using lifter
The cathode of constant voltage power supply connect with cathode, connect anode with anode, implements cell reaction below by circulation.Each stream
The rate of circulating flow of body in terms of linear velocity, make cathode side 1m/ minutes, anode-side is 3m/ minutes.
<embodiment 2>
By the surface of the anode-side of dielectric film carry out it is further provided for contouring implement hydrophilicity-imparting treatment, in addition to this, formed with it is real
Apply the equivalent electrolytic cell of example 1.Concave-convex maximum height is 10 μm.
<embodiment 3>
The surface of the anode-side of dielectric film is ground with No. 2000 sand paper, and then is formed with 5 μ m thicks
Zirconium oxide layer implements hydrophiling, in addition to this, forms the electrolytic cell being equal with embodiment 1.Concave-convex maximum height is 15 μm.
<comparative example 1>
Do not implement hydrophilicity-imparting treatment, in addition to this, forms the electrolytic cell being equal with embodiment 1.
<comparative example 2>
Do not implement hydrophilicity-imparting treatment, the thickness of spacer is set as 50 μm, in addition to this, what formation was equal with embodiment 1
Electrolytic cell.
<comparative example 3>
Do not implement hydrophilicity-imparting treatment, the thickness of spacer is set as 200 μm, in addition to this, what formation was equal with embodiment 1
Electrolytic cell.
(performance evaluation)
Fig. 2 is that the electric current of the electrolytic cell of the embodiment 1,2 when showing the output voltage 2.0V for making constant voltage power supply is close
The figure of the ongoing change of the current density of the electrolytic cell of the ongoing change and comparative example 1 of degree.It is real although being identical voltage
Apply the available high current density compared with comparative example of example 1,2.In addition, comparative example 1 is initially confirming big voltage reduction.
It is possible thereby to investigate, compared with comparative example 1, the oxygen generated in anode-side is discharged to top without being attached to embodiment 1,2
Therefore dielectric film will not cause the current convergence of the part on dielectric film and block along with anode side gas excessively electric
Pressure rises, available high current density.In addition, having no, which becomes unstable by the current potential of cathode side, is led in embodiment 1,2
The instantaneous hydrogen caused generates (reduction to the faradic efficiency of organic matter reduction), and the anode state in cell reaction is good, by
This confirmed cathode reaction it is also preferred that carrying out.
Fig. 3 is the current density and ratio for showing the electrolytic cell for the embodiment 3 for making decomposition voltage from 0.6V frequency sweep to 3.8V when
Compared with the figure of the current density of the electrolytic cell of example 1~3.Embodiment 3 is low voltage throughout low current domain to high current field.Relatively
In this, in comparative example 2,3, in 200mA/cm2When above, electric current sharp rises in vibration, cell voltage.It is thought that by
In the influence of the oxygen bubble generated in anode.Spacer is set as 25 μm and carries out the comparative example 1 of hydrophiling to dielectric film
Polarization curve in, more than 300mA/cm2Until also have no the vibration of cell voltage.It is thus regarded that by the way that dielectric film is carried out
Hydrophiling, so that the hydrogen slightly generated in the oxygen or cathode that generate in anode is suppressed the attachment of dielectric film, gas
Discharge is promoted, therefore resistance reduces, in addition, being suppressed by the reaction concentration caused by bubble, overvoltage is reduced, and can be dropped
Low electrolytic cell voltage.
<embodiment 4>
By hydrophobic carbon black (electrochemical industry Co. Ltd. system AB-6) and PTFE water slurry (Mitsui
Fluorochemicals Company 31JR) mixing, dissolved with the TRITON's (registered trademark) for being equivalent to 20 mass %
After being sufficiently stirred in water, gained mixing suspension is reached into 108g/m with the quality of the carbon black of unit projection area2Side
Formula is coated on the carbon cloth (Ballard corporation) of thickness 0.4mm, as cathode substrate.Then, by hydrophobic carbon black (electrochemistry
Industrial Co., Ltd AB-6), hydrophilic carbon black (electrochemical industry Co. Ltd. system AB-12), Pt-Ru particle and Nafion liquid
(Mitsui Fluorochemicals Company 31JR) mixing, by the mixing suspension with the catalysis of unit projection area
Agent quality becomes 0.5mg/cm2Mode be coated on the cathode substrate of thickness 0.5mm.Later, it is dried at 60 DEG C, in electricity
In furnace with 305 DEG C carry out 15 minutes roast, pressure processing is carried out at pressure 0.6MPa, with the filling rate of gas diffusion cathode at
For 40% mode, cathode is made.
The two sides of dielectric film is ground and hydrophiling in a manner of forming 2 μm concave-convex, using the film, assembling with
The same electrolytic cell of embodiment 1.Into anode with 10mL/ minutes importing 1M aqueous sulfuric acids, led into cathode with 5mL/ minutes
Enter toluene, battery temperature is set as 60 DEG C and is 400mA/cm2When, cell voltage 2.15V.Until areas of high current density is
Only cell voltage does not vibrate.Current efficiency is 95%.
<embodiment 5>
Hydrophiling only is carried out to the anode-side of dielectric film and in addition to this makes electrolytic cell similarly to Example 4, into
Row performance measurement, as a result 400mA/cm2When be 2.2V.In addition, having no the vibration of cell voltage until areas of high current density
It is dynamic.Current efficiency is 95%.
<comparative example 4>
Hydrophiling is not carried out to dielectric film, in addition to this, makes electrolytic cell similarly to Example 4, carry out performance survey
Determine, as a result 300mA/cm2When be 2.2V.The vibration of visible cell voltage in areas of high current density.Current efficiency is 90%.
The present invention is not limited to above embodiment, the common sense based on those skilled in the art can also be subject to various set
Deformation, the embodiments that joined such deformation such as meter change also may include in the scope of the present invention.
Description of symbols
Electrolytic cell (electrolytic cell) is used in the manufacture of 10 organic chemistry hydride
11 solid polyelectrolyte membranes (dielectric film)
12 cathodes
12a cathode substrate
12b cathode catalyst layer
12c cathode support body
13 cathode chambers
13a partition
13b spacer
14 anodes (anode) containing electrode catalyst
14a anode-supported elastomer
15 anode chambers
15a partition
15b spacer
16 anode spacers
17 are hydrogenated object entrance
The outlet of 18 hydride
19 acidic electrolysis bath entrances
The outlet of 20 acidic electrolysis baths
Claims (1)
1. a kind of organic chemistry hydride manufacture electrolytic cell, has: the solid macromolecule electrolyte with proton-conducting
Film；Cathode is set to a face of the solid polyelectrolyte membrane and will be hydrogenated object reduction and generate hydride；Yin
Pole room, stores the cathode and is supplied to and be hydrogenated object；Anode containing electrode catalyst is set to the solid macromolecule
Another face of dielectric film and water oxygen is generated into proton；With anode chamber stores the anode and is supplied to electrolysis
Liquid, the organic chemistry hydride manufacture electrolytic cell be characterized in that,
At least described anode-side surface of the solid polyelectrolyte membrane has carried out hydrophiling,
As the hydrophiling, the surface of the solid polyelectrolyte membrane is implemented it is further provided for contouring, by further provided for contouring face
JIS B 0601 in maximum height be 2~30 μm.
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| JP2014-195202 | 2014-09-25 | ||
| JP2014195202A JP6400410B2 (en) | 2014-09-25 | 2014-09-25 | Electrolysis cell for organic chemical hydride production |
| PCT/JP2015/076769 WO2016047629A1 (en) | 2014-09-25 | 2015-09-18 | Electrolytic cell for production of organic chemical hydrides |
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| US (1) | US11236428B2 (en) |
| EP (1) | EP3199665B1 (en) |
| JP (1) | JP6400410B2 (en) |
| KR (1) | KR20170063694A (en) |
| CN (1) | CN106715759B (en) |
| CA (1) | CA2962180C (en) |
| DK (1) | DK3199665T3 (en) |
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| CN106133199A (en) * | 2014-03-28 | 2016-11-16 | 国立大学法人横浜国立大学 | Organic hydride material producing device |
| CN107002262B (en) * | 2014-11-10 | 2019-10-29 | 国立大学法人横浜国立大学 | Oxygen anode |
| JP6501141B2 (en) * | 2014-11-21 | 2019-04-17 | 国立大学法人横浜国立大学 | Organic hydride manufacturing apparatus and method of manufacturing organic hydride using the same |
| JP2019056136A (en) * | 2017-09-20 | 2019-04-11 | 株式会社東芝 | Electrochemical reaction device |
| JP7273929B2 (en) * | 2017-09-20 | 2023-05-15 | 株式会社東芝 | Electrochemical reactor and porous separator |
| KR20190083546A (en) | 2018-01-04 | 2019-07-12 | (주)엘켐텍 | Electrochemical hydrogenation reactor and method of hydrogenation using the same |
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| AU2021215607A1 (en) | 2020-02-06 | 2022-08-25 | AGC Inc. | Ion Exchange Membrane with Catalyst Layer, Ion Exchange Membrane and Electrolytic Hydrogenation Apparatus |
| JP6818920B2 (en) * | 2020-02-12 | 2021-01-27 | 株式会社東芝 | Electrochemical reactor |
| WO2022050363A1 (en) * | 2020-09-04 | 2022-03-10 | Ａｇｃ株式会社 | Membrane electrode assembly, solid polymer electrolyte membrane, waer electrolysis system and electrolytic hydrogenation system |
| JP7345527B2 (en) * | 2021-09-13 | 2023-09-15 | 株式会社Ｓｃｒｅｅｎホールディングス | Membrane electrode assembly, hydrogen production device, catalyst ink manufacturing method, and membrane electrode assembly manufacturing method |
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| WO2016047629A1 (en) | 2016-03-31 |
| DK3199665T3 (en) | 2020-09-28 |
| EP3199665A4 (en) | 2018-05-30 |
| ES2822185T3 (en) | 2021-04-29 |
| EP3199665B1 (en) | 2020-09-02 |
| CN106715759A (en) | 2017-05-24 |
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| US20170292198A1 (en) | 2017-10-12 |
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